|Publication number||US4490302 A|
|Application number||US 06/554,880|
|Publication date||Dec 25, 1984|
|Filing date||Nov 25, 1983|
|Priority date||Nov 25, 1983|
|Also published as||CA1216855A, CA1216855A1|
|Publication number||06554880, 554880, US 4490302 A, US 4490302A, US-A-4490302, US4490302 A, US4490302A|
|Inventors||Eric C. Ma, James N. Rieck|
|Original Assignee||Mobay Chemical Corporation|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (23), Referenced by (23), Classifications (12), Legal Events (5)|
|External Links: USPTO, USPTO Assignment, Espacenet|
Diisocyanates which are liquid at room temperature have numerous advantages over solid diisocyanates. Diisocyanates which are liquid at room temperature, such as toluene diisocyanate or hexamethylene diisocyanate, are, as a rule, physiologically harmful because of their high vapor pressure. For this reason, various attempts have been made to start with diisocyanates that are solid at room temperature and convert these into the liquid form by certain measures.
The most commercially important diisocyanates which are solid at room temperature are 4,4'-diphenylmethane diisocyanate and the 2,4'-isomer thereof, which melt at 39° C. and 34.5° C., respectively.
Numerous patents have issued relating to the liquification of diphenylmethane diisocyanate. See, for example, U.S. Pat. Nos. 3,152,162; 3,384,653; 3,394,165; 3,449,256; 3,640,966; 3,641,093; 3,674,828; 3,701,796; 3,883,571; 4,014,935; 4,055,548; 4,088,665; 4,031,026; 4,102,833; 4,115,429; 4,118,411; 4,154,752; 4,177,205; 4,229,347; 4,261,852; 4,321,333; and 4,332,742.
One of the more commercially successful liquid diphenylmethane diisocyanate compositions is produced according to U.S. Pat. No. 3,644,457. These isocyanates are prepared by reacting 4,4'- and/or 2,4'-diphenylmethane diisocyanate with a branched aliphatic dihydroxy compound to produce a product which is liquid at room temperature. According to this patent, 1 mol of a diphenylmethane diisocyanate is reacted with from about 0.1 to about 0.3 mols of a poly-1,2-propylene ether glycol having a molecular weight of from 134 to 700.
Although the isocyanates made according to U.S. Pat. No. 3,644,457 have met with significant commercial success, such isocyanates are generally linear in structure (i.e., having NCO functionalities of 2). For many applications, it would be desirable to provide liquid diphenylmethane diisocyanate compositions having some branching (i.e., having NCO functionalities of greater than 2). Additionally, for some applications it would be desirable to incorporate some unsaturation in the isocyanate composition.
It is an object of the present invention to provide improved organic isocyanates which are liquid at room temperature and which remain liquid even on prolonged storage down to 15° C. Another object of this invention is to provide an improved process for preparing such liquid organic isocyanates. Finally, it is an object of this invention to provide a liquid isocyanate which has some branching and which may have some incorporated unsaturation.
The present invention is directed to a liquid, diphenylmethane diisocyanate having an isocyanate functionality of greater than 2 (and generally less than 2.20) and an isocyanate group content of from about 20 to about 30 percent by weight, prepared by reacting
(a) diphenylmethane diisocyanate, with
(b) a mixture of
(i) from about 5 to about 20 equivalent percent of a monohydroxy alcohol,
(ii) from about 25 to about 35 equivalent percent of a poly-1,2-propylene ether glycol having a molecular weight of from 134 to 700, and
(iii) from about 45 to about 65 equivalent percent of a trihydroxy alcohol selected from the group consisting of trimethylolpropane, triethylolpropane, glycerine, and 1,3,6-hexane triol,
the total equivalent percent of (i), (ii) and (iii) being 100, and wherein the weight ratio of (a) to (b) is from 5:1 to 15:1.
In general, the components are reacted at a temperature of from about 40° C. to about 90° C., preferably from 40° C. to about 75° C., and most preferably from about 50° C. to about 70° C. The preferred isocyanate group content is from about 20 percent to about 25 percent by weight, while the preferred weight ratio of component (a) to component (b) is from about 6:1 to about 10:1.
The liquid modified diphenylmethane diisocyanate may also be prepared as a concentrate (that is, with a lower percent isocyanate group content) and diluted with additional diphenylmethane diisocyanate to adjust the isocyanate content to the desired level.
The present invention is also directed to a process for producing the above-noted isocyanate compositions by reacting the diphenylmethane diisocyanate with the mixture noted above. As used herein the term "diphenylmethane diisocyanate" is defined as 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate and mixtures thereof.
The liquid isocyanates which can be prepared according to the invention preferably from 4,4'- and/or 2,4'-diphenylmethane diisocyanate, have a low viscosity and can therefore be processed very easily. Additionally, they have a very low vapor pressure and are, therefore, less physiologically harmful. In addition, the resultant products can be used in the reaction injection molding (RIM) process, in shoe sole formulations, in adhesives and in zinc coatings to yield better overall properties in the resultant polyurethane and/or polyurea product. In the RIM process, improved green strength of the molded product is achieved using the isocyanates of the present invention.
In general, the process may be carried out by introducing the mixture of components containing isocyanate-active hydrogen groups into the isocyanate at temperatures of from about 40° to about 90° C., with stirring. The isocyanate content of the product of the process amounts to from about 20 to about 30 percent, by weight, and preferably to from about 20 to about 25 percent, by weight.
Suitable monohydroxy alcohols include substantially any saturated or unsaturated monohydroxy alcohol. Such alcohols preferably have molecular weights of from 32 to 270 and include aliphatic, unsaturated aliphatic, substituted aliphatic, aromatic, alicyclic and heterocyclic alcohols. They may be primary, secondary or tertiary alcohols. Examples of n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-amyl, sec-amyl, diethylcarbinol, d-amyl, n-hexyl, n-heptyl, 2-heptyl, 4-heptyl (4-heptanol), n-octyl, sec-n-octyl, n-nonyl, n-decyl, n-undecyl, lauryl, myristyl, cetyl and stearyl alcohol. Additionally, vinyl, allyl, propargyl(2-propyn-1-ol), crotyl, oleyl, benzyl, α-phenylethyl, β-phenylethyl, phenylpropyl(3-phenyl-1-propanol), α-methylbenzyl, cinnamyl, anisyl, furfuryl and tetrahydrofurfuryl alcohols may be used. Further examples of suitable alcohols include citronellol, geraniol, linalool, cyclopentanol, cyclohexanol, menthol, -terpineol, borneol, benzohydrol, triphenyl-carbinol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 2-octanol, 2-ethyl-1-hexanol, 1-decanol, 5-ethyl-2-nonanol, 1-dodecanol, 1-tetradecanol, 7-ethyl-2-methyl-4-undecanol, 1-hexadecanol, 3,9-diethyl-6-tridecanol and 2-hydroxy ethylmethacrylate.
The presently preferred monohydroxy alcohols are cinnamyl alcohol; 3-phenyl-1-propanol; 4-heptanol; propargyl alcohol; 2-hydroxy ethyl methacrylate; and tert-butanol.
The poly-1,2-propylene ether glycols useful herein include dipropylene glycol, tripropylene glycol and higher propylene glycols, with tripropylene glycol being presently preferred.
The presently preferred trihydroxy alcohol is trimethylol propane.
As noted above, the amounts of mono-alcohol, poly-1,2-propylene ether glycol and trihydroxy alcohol are within certain specified ranges. The various equivalent percents can be readily determined by first equivalent percents can be readily determined by first adding the total hydroxy equivalents in the mixture. The hydroxyl equivalents represented by any one component of the mixture can then be divided by the total equivalent to arrive at an equivalent percent for the mixture.
The products of the present invention can be used for many different polyaddition reactions in the lacquer and plastics industry. For example, they may be used in the products of polyurethane foams and elastomers, such as in reaction injection molding (RIM) products, shoe soles, adhesives and coatings, to give better physical properties, especially green strength, when compared to known modified diphenylmethane diisocyanates.
The invention is further illustrated, but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
In each of Examples 1-9, trimethylol propane (TMP) was dissolved, over a one-to-one-and-one-half hour period, in tripropylene glycol (TPG) and a monohydroxy alcohol at 70° C. The mixture thus formed was added to 4,4'-diphenylmethane diisocyanate in a flask over which nitrogen gas was passed. Ice water was circulated around the flask to control the rapid increase in temperature observed, and the reaction continued, at 65° C., for three-and-one-half hours.
The amounts and equivalent percents of TMP, TPG, monohydroxy alcohol, and the amounts of MDI were as indicated in Table 1. The characteristics of the resulting liquid diphenylmethane diisocyanate Examples 1 through 9 were clear liquids while those of Examples 10 and 11 (both comparison examples) were hazy liquids.
TABLE I__________________________________________________________________________Com- Example #1ponents 1 2 3 4 5 6 7 8 9 10 11__________________________________________________________________________TMP, pbw 78 52 60 60 60 60 60 78 150 8 8equivalent 54 49 56 59 56 56 54 63 58 53 56percentTPG, pbw 104 78 72 72 72 72 72 74.1 180 12 12equivalent 34 34 31 33 31 31 30 28 33 38 40percentCinnamyl 52 52 42 24 -- -- -- 35 73.9 4 1Alcohol,pbwequivalent 12 17 13 8 -- -- -- 9 9 9 3percentPropargyl -- -- -- -- -- -- 21.9 -- -- -- --Alcohol,pbwequivalent -- -- -- -- -- -- 16 -- -- -- --percent3-phenyl-1- -- -- -- -- 42 -- -- -- -- -- --propanol,pbwequivalent -- -- -- -- 13 -- -- -- -- -- --percent4-heptanol, -- -- -- -- -- 36.3 -- -- -- -- --pbwequivalent -- -- -- -- -- 13 -- -- -- -- --percentMDI, pbw 1300 1300 1200 1200 1200 1200 1200 1200 3000 200 200WeightRatioMDI: Mix- 5.6:1 7.1:1 6.9:1 7.7:1 6.9:1 7.1:1 7.8:1 6.4:1 7.4:1 8.3:1 9.5:1ture ofTMP,TPGand Mono-alcoholProductCharacter-isticsViscosity, 26500 1030 2600 1750 1800 2000 2800 1500 1650 NOT NOTcps at 24.2° C. 24.2° C. 25.5° C. 23.5° C. 26.4° C. 25° C. 23.5° C. 25.5° C. 24.5° C. TESTED TESTED% NCO, 19.7 23.05 22.06 22.93 22.11 22.28 22.4 20.8 22.6actual% NCO, 19.7 22.8 22 22.73 22.03 22.11 22.1 20.7 22.5calculatedNCO -- 2.06 2.085 2.097 2.085 2.085 2.078 2.119 2.094Func-tionalityFreezing 14 14 14 15 14 14 14 13 14Point, °C.__________________________________________________________________________
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US3152162 *||Jul 20, 1960||Oct 6, 1964||Bayer Ag||Polyisocyanate-carbodiimide adducts and process for the production thereof|
|US3384653 *||Mar 31, 1965||May 21, 1968||Upjohn Co||Compositions of methylenebis (phenyl isocyanate) with trihydrocarbyl phosphates and preparation thereof|
|US3394165 *||Oct 24, 1965||Jul 23, 1968||Upjohn Co||Stabilized methylenebis-(phenyl isocyanate) compositions|
|US3449256 *||Jan 19, 1966||Jun 10, 1969||Upjohn Co||Methylenebis(phenyl isocyanate) compositions and preparation thereof|
|US3640966 *||Jan 23, 1969||Feb 8, 1972||Bayer Ag||Process for the preparation of polyisocyanates which contain a carbodiimide-isocyanate adduct|
|US3641093 *||Nov 4, 1968||Feb 8, 1972||Ici Ltd||Stable liquid diphenylmethane diisocyanates|
|US3644457 *||Feb 28, 1968||Feb 22, 1972||Bayer Ag||Preparation of stable liquid diphenylmethane diisocyanates|
|US3674828 *||May 2, 1969||Jul 4, 1972||Ici Ltd||Preparation of liquid diphenylmethane diisocyanate compositions|
|US3701796 *||Sep 29, 1970||Oct 31, 1972||Upjohn Co||Storage stable methylenebis (phenyl isocyanate) compositions|
|US3883571 *||Sep 10, 1973||May 13, 1975||Ici Ltd||Liquid diphenylmethane diisocyanate compositions|
|US4014935 *||Mar 25, 1976||Mar 29, 1977||Imperial Chemical Industries Limited||Carbodiimides|
|US4031026 *||May 10, 1976||Jun 21, 1977||Imperial Chemical Industries Limited||Diphenylmethane diisocyanate compositions|
|US4055548 *||Sep 17, 1976||Oct 25, 1977||The Upjohn Company||Storage-stable liquid polyisocyanate composition|
|US4088665 *||Aug 17, 1976||May 9, 1978||Bayer Aktiengesellschaft||Process for the partial carbodiimidization of organic isocyanates|
|US4102833 *||Mar 16, 1977||Jul 25, 1978||Mccord Corporation||Cold impact resistant urethane foam|
|US4115429 *||Mar 18, 1977||Sep 19, 1978||Mobay Chemical Corporation||Low-temperature storage stable liquid diphenylmethane diisocyanates|
|US4118411 *||Feb 9, 1977||Oct 3, 1978||Mobay Chemical Corporation||Low-temperature storage stable liquid diphenylmethane diisocyanates|
|US4154752 *||May 5, 1978||May 15, 1979||Mobay Chemical Corporation||Preparation of partially carbodiimidized methylenebis (phenyl isocyanate)|
|US4177205 *||Nov 20, 1978||Dec 4, 1979||Basf Wyandotte Corporation||Process for the preparation of highly stable liquid carbodiimide-containing polyisocyanate compositions|
|US4229347 *||Mar 28, 1979||Oct 21, 1980||Imperial Chemical Industries Limited||Liquid diphenylmethane diisocyanate compositions|
|US4261852 *||Oct 1, 1979||Apr 14, 1981||Imperial Chemical Industries Limited||Liquid polyisocyanate compositions|
|US4321333 *||Apr 16, 1981||Mar 23, 1982||The Upjohn Company||Polyurethane prepared from polyisocyanate blend|
|US4332742 *||Jun 22, 1981||Jun 1, 1982||Mobay Chemical Corporation||Low temperature storage stable liquid diphenylmethane diisocyanates|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US4576731 *||Jan 17, 1983||Mar 18, 1986||Mobay Chemical Corporation||Conversion of incompatible mixed polyols to polyol products with increased resistance to phase separation|
|US4883909 *||May 11, 1988||Nov 28, 1989||Mobay Corporation||Liquid diphenylmetane diisocyanate compositions|
|US4910333 *||Jun 3, 1987||Mar 20, 1990||Mobay Corporation||Liquid diphenylmethane diisocyanate compositions|
|US5001208 *||Mar 20, 1989||Mar 19, 1991||Reeves Brothers, Inc.||Linear polyurethane elastomer compositions based on mixed polycarbonate and polyether polyols|
|US5013811 *||Mar 20, 1989||May 7, 1991||Reeves Brothers, Inc.||Use of modified diisocyanates for preparing linear thermoplastic polyurethane elastomers having improved properties|
|US5096992 *||May 3, 1991||Mar 17, 1992||Reeves Brothers, Inc.||Use of modified diisocyanates for preparing linear thermoplastic polyurethane elastomers having improved properties|
|US5110666 *||May 6, 1991||May 5, 1992||Reeves Brothers, Inc.||Coated fabric structure for air bag applications|
|US5130384 *||Mar 20, 1989||Jul 14, 1992||Reeves Brothers, Inc.||Calenderable thermoplastic polyurethane elastomer compositions containing millable linear polyurethanes|
|US5288899 *||Jun 30, 1993||Feb 22, 1994||Miles Inc.||Liquification of diphenylmethane diisocyanate by partially reacting the isocyanate groups with blocking agents|
|US5298303 *||Nov 6, 1991||Mar 29, 1994||Reeves Brothers, Inc.||Fabric structure for severe use applications|
|US5350778 *||Oct 28, 1993||Sep 27, 1994||Miles Inc.||Polyisocyanate based upon 4,4'- and 2,4'-diphenylmethane diisocyanates and use thereof in a rim process|
|US5563232 *||Feb 7, 1995||Oct 8, 1996||Bayer Corporation||Rim process utilizing isocyanates based upon 2,4'- and 4,4'-diphenylmethane diisocyanate|
|US5585452 *||Jun 6, 1995||Dec 17, 1996||Bayer Corporation||Polyisocyanate based upon 4,4'-and 2,4'-diphenyl-methane dllsocyanates and use thereof in a rim process|
|US5686042 *||Jun 7, 1995||Nov 11, 1997||Bayer Corporation||Rim process using liquid methylene diphenyl diisocyanate|
|US6376567||Dec 7, 2000||Apr 23, 2002||Bayer Corporation||Polyisocyanate compositions and a process for the production of low-density flexible foams with low humid aged compression sets from these polyisocyanate compositions|
|US6482913||Feb 7, 2000||Nov 19, 2002||Bayer Aktiengesellschaft||Liquid MDI adducts wtih improved freeze stability|
|US6777026||Oct 7, 2002||Aug 17, 2004||Lord Corporation||Flexible emissive coatings for elastomer substrates|
|US20040068036 *||Oct 7, 2002||Apr 8, 2004||Halladay James R.||Flexible emissive coatings for elastomer substrates|
|US20040077773 *||Jul 11, 2003||Apr 22, 2004||Tavares Manuel J||Low viscosity, flexible, hydrolytically stable potting compounds|
|US20090156777 *||Dec 17, 2007||Jun 18, 2009||Nodelman Neil H||Freeze-stable aromatic diisocyanates and processes for the preparation of these freeze-stable products|
|CN101906204B *||Jul 17, 2008||Aug 10, 2016||广东华润涂料有限公司||作为聚氨酯涂料固化剂的基于二苯基甲烷二异氰酸酯的预聚体及其制备方法|
|EP0415159A2 *||Aug 11, 1990||Mar 6, 1991||Bayer Ag||Liquid polyisocyanate mixtures, process for their preparation and their use for the preparation of polyurethane foams|
|WO2009078984A2||Dec 16, 2008||Jun 25, 2009||Bayer Materialscience Llc||Freeze-stable aromatic diisocyanates and processes for the preparation of these freeze-stable products|
|U.S. Classification||558/330, 521/159, 521/155, 558/359, 560/26, 560/27|
|Cooperative Classification||C08G18/8035, C08G2120/00, C08G18/8064|
|European Classification||C08G18/80B3D8, C08G18/80H2|
|Aug 20, 1984||AS||Assignment|
Owner name: MOBAY CHEMICAL CORPORATION, PITTSBURGH PA A CORP O
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:MA, ERIC C.;RIECK, JAMES N.;REEL/FRAME:004290/0174
Effective date: 19831118
Owner name: MOBAY CHEMICAL CORPORATION,PENNSYLVANIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MA, ERIC C.;RIECK, JAMES N.;REEL/FRAME:004290/0174
Effective date: 19831118
|Jan 21, 1988||FPAY||Fee payment|
Year of fee payment: 4
|Jul 28, 1992||REMI||Maintenance fee reminder mailed|
|Dec 27, 1992||LAPS||Lapse for failure to pay maintenance fees|
|Mar 9, 1993||FP||Expired due to failure to pay maintenance fee|
Effective date: 19921227